KR20170116232A - Element-sealing resin composition for organic electronic device, element-sealing resin sheet for organic electronic device, organic electroluminescence element, and image display apparatus - Google Patents

Abstract

Disclosure of the Invention An object of the present invention is to provide an organic electroluminescence device capable of achieving a balance between water vapor barrier property and adhesive force and at the same time lowering the water content and sufficiently suppressing the generation of outgas, A resin composition for device sealing, a resin sheet for sealing an organic electronic device, an organic electroluminescence element, and an image display are provided. The resin composition for sealing an organic electronic device of the present invention contains a polyisobutylene resin (A) having a weight average molecular weight (Mw) of 10,000 to 300,000 and a hydrogenated cyclic olefin polymer (B) Is 500 ppm or less, and the amount of outgas generated when heated at 85 占 폚 for 1 hour is 500 ppm or less.

Description

TECHNICAL FIELD [0001] The present invention relates to a resin composition for sealing an organic electronic device, a resin sheet for sealing an organic electronic device, an organic electroluminescence element, and an image display device. , ORGANIC ELECTROLUMINESCENCE ELEMENT, AND IMAGE DISPLAY APPARATUS}

The present invention relates to a resin composition for sealing an organic electronic device, a resin sheet for sealing an element for an organic electronic device, an organic electroluminescence element, and an image display device used for sealing an organic electronic device element.

Recently, various organic electronic devices such as organic electroluminescence display (hereinafter also referred to as " organic EL ") display, organic EL lighting, organic semiconductor and organic solar cell have been actively studied and liquid crystal displays Display, and LCD), and next-generation displays that replace light-emitting diodes (LEDs). In addition, organic EL devices can be used as flexible displays or lights because all components can be formed of solid materials. The organic EL element is based on a constitution in which an ITO (Indium Tin Oxide) transparent electrode (anode), an organic film (organic hole transporting layer, organic luminescent layer or the like) and a metal electrode (cathode) are formed on a glass substrate, The layers are energized to emit self-luminescence.

However, it is known that an organic EL element is weak against an organic gas (hereinafter also referred to as " outgas ") generated from water or a constituent member.

Therefore, attempts have been made to prevent deterioration of the organic EL element by placing the organic EL element in an atmosphere excluding water or minimizing the outgassing from the constituent elements for the long life of the organic EL element.

For example, as a method of maintaining moisture-free atmosphere, a sealing composition comprising a hydrogenated cycloolefin-based polymer and a polyisobutylene resin having a weight average molecular weight of more than 500,000 has been proposed (see, for example, Patent Document 1 Reference). Further, a pressure-sensitive adhesive composition which suppresses lowering of steam vapor barrier property and also has excellent peel strength is proposed by selecting a material having a viscosity average molecular weight (Mv) of 300,000 to 500,000 and a lower molecular weight in consideration of prevention of deterioration of peel strength See Patent Document 2).

Japanese Patent No. 5074423 Japanese Patent Laid-Open Publication No. 193335

However, in the inventions described in Patent Documents 1 and 2, deterioration of the element for organic electronic devices can not be prevented when the water vapor barrier property is high but the water content and the amount of generated outgas are large. Further, since the adhesive force to the adherend is not sufficient, the lifetime of the device for organic electronic devices has been limited. In addition, the invention described in the above Patent Documents 1 and 2 has a problem in that, when sealed, air bubbles enter the adherend and damage the appearance of the adherend because the adherability to the adherend is poor.

Accordingly, it is an object of the present invention to provide an organic electroluminescent device which can balance the water vapor barrier property and the adhesive force, and can sufficiently suppress the generation of outgas by lowering the water content and consequently sufficiently lengthening the device for organic electronic devices, An organic electroluminescence device, and an image display device, which are capable of being used as an organic electroluminescent device.

In order to solve the above problems, the resin composition for sealing an organic electronic device according to the present invention comprises a polyisobutylene resin (A) having a weight average molecular weight (Mw) of 10,000 to 300,000 and a hydrogenated cyclic olefin polymer ), The water content by the Karl Fischer method is 500 ppm or less, and the outgassing amount when heated at 85 캜 for 1 hour is 500 ppm or less.

Wherein the resin composition for sealing an organic electronic device has a weight ratio (A) :( (A)) of the polyisobutylene resin (A) having a weight average molecular weight (Mw) of 10,000 to 300,000 and the hydrogenated cycloolefin polymer B) is in the range of 90:10 to 20:80.

It is also preferable that the hydrogenated cycloolefin polymer is a hydride of a C5-based petroleum resin, a hydride of a C9-based petroleum resin, or a hydride of a petroleum resin obtained by copolymerizing a C5-based petroleum resin and a C9-based petroleum resin.

The resin composition for sealing an organic electronic device preferably has a loss elastic modulus at 60 캜 of 100,000 Pa 占 퐏 or less.

In addition, it is preferable that the resin composition for sealing an organic electronic device further comprises an organometallic or metal oxide based desiccant.

In the resin composition for sealing an organic electronic device, it is preferable that the organic metal-based or metal oxide-based drying agent is contained in an amount of 1 wt% to 50 wt% with respect to the total weight of the resin composition.

The resin composition for sealing an organic electronic device preferably has a light transmittance of 85% or more with respect to light having a wavelength of 550 nm at a thickness of 0.1 mm.

In order to solve the above problems, the resin sheet for sealing an organic electronic device according to the present invention has at least a sealing layer formed of the resin composition for sealing an organic electronic device according to any one of the above.

In order to solve the above problems, an organic electroluminescence device according to the present invention is characterized by being sealed with a resin composition for sealing an organic electronic device according to any one of the above.

The image display apparatus according to the present invention is characterized by having the organic electroluminescence element.

INDUSTRIAL APPLICABILITY The resin composition for encapsulating an element for an organic electronic device and the resin sheet for encapsulating an element for an organic electronic device according to the present invention have sufficiently low vapor-barrier properties and can sufficiently inhibit generation of outgassing, The number of organic EL elements can be increased. In addition, since it can follow the adherend well, air bubbles do not enter the adherend when it is sealed, and the appearance is excellent.

1 is a cross-sectional view schematically showing the structure of a resin sheet for sealing an organic electronic device according to an embodiment of the present invention.
2 is a cross-sectional view schematically showing the structure of an image display apparatus using a resin sheet for sealing an organic electronic device according to an embodiment of the present invention.
3 is an explanatory diagram for schematically explaining an example of use of a resin sheet for sealing an organic electronic device according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail.

In the resin sheet (1) for sealing an organic electronic device for an organic electronic device according to the embodiment of the present invention, at least one sealing layer (3) is formed on at least one side of the base sheet (2). 1 is a schematic cross-sectional view showing a preferred embodiment of a resin sheet 1 for sealing an element for an organic electronic device according to the present invention. 1, a resin sheet 1 for sealing an element for an organic electronic device has a base sheet 2, and a sealing layer 3 is formed on the base sheet 2. As shown in Fig. The resin sheet 1 for sealing an organic electronic device further includes a release film 4 for protecting the sealing layer 3 on the sealing layer 3.

Hereinafter, each component of the resin sheet 1 for sealing an organic electronic device according to the present embodiment will be described in detail.

(Substrate sheet 2, release film 4)

The base sheet (2) temporarily adheres the resin composition for the purpose of improving handleability when the resin composition constituting the sealing layer (3) is formed into a film. The release film 4 is also used for the purpose of protecting the sealing layer 3.

The base sheet 2 and the release film 4 are not particularly limited and examples thereof include a polyethylene film, a polypropylene film, a polybutene film, a polybutadiene film, a polymethylpentene film, a polyvinyl chloride film, a vinyl chloride copolymer film , Ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylate copolymer film, polyethylene terephthalate film, polyethylene naphthalate film, polybutylene terephthalate film, polyurethane film, ethylene / vinyl acetate copolymer film, ionomer resin film, Acrylic acid ester copolymer film, polystyrene film, polycarbonate film, polyimide film, and fluororesin film. These crosslinked films are also used. It may also be a film of these laminated layers. Particularly, it is preferable to use polyethylene terephthalate in terms of cost, handling property and the like.

The release paper coated with the release agent on the paper reaches the sealing layer 3 through the water vapor through the paper base material, so that the sealing layer 3 absorbs moisture, and the moisture from the sealing layer 3 to the organic electronic device It is not preferable as the base sheet 2 and the release film 4 because the organic electronic device becomes deteriorated to accelerate deterioration of the organic electronic device. Also, the release paper coated with a release agent on paper is not preferable from the standpoint that the amount of outgas generated when heated at 85 캜 for one hour increases.

An example of the peeling force when peeling the sealing layer 3 from the base sheet 2 and the release film 4 is preferably 0.3 N / 20 mm or less, and more preferably 0.2 N / 20 mm. The lower limit of the peeling force is not particularly limited, but is more than 0.005 N / 20 mm. Further, when the release film is temporarily adhered to both surfaces, it is preferable to use one having a different peeling force to improve handling properties.

The thickness of the base sheet 2 and the release film 4 is usually 5 to 300 탆, preferably 10 to 200 탆, particularly preferably 20 to 100 탆.

(Sealing layer 3)

The resin composition for sealing an organic electronic device of the present invention constituting the sealing layer (3) is obtained by mixing a polyisobutylene resin (A) having a weight average molecular weight (Mw) of 10,000 to 300,000 and a hydrogenated cycloolefin polymer ), The water content by the Karl Fischer method is 500 ppm or less, and the outgassing amount when heated at 85 占 폚 for 1 hour is 500 ppm or less.

[Polyisobutylene resin (A)]

The polyisobutylene resin (A) is generally a resin having a polyisobutylene skeleton in the main chain or side chain, and is not particularly limited as long as the weight average molecular weight (Mw) is 10,000 to 300,000. The polyisobutylene resin (A) comprises a copolymer of an isobutylene monomer and one or more olefins, preferably a conjugated olefin, as a comonomer. The polyisobutylene resin is usually prepared by a slurry method using a methylene chloride as a medium and a Friedel-Crafts catalyst as a part of a polymerization initiator. Such a polyisobutylene resin is characterized by high water vapor barrier property and high tackiness.

Examples of the polyisobutylene resin (A) suitable for the present invention include a thermosetting resin such as a polysulfone or an opanol (B10, B12, B15, B50, B80, B100, B120, B150, B220 etc.) manufactured by BASF, Tetramethyl (3T, 4T, 5T, 6T etc.), hydrom (4H, 5H, 6H and the like) manufactured by Nisseki Energy K.K. and butyl rubber manufactured by Nippon Budaku Co., These may be used alone, or two or more kinds may be used in combination by adjusting viscosity.

The polyisobutylene resin (A) has a weight average molecular weight (Mw) of 10,000 to 300,000. When the weight average molecular weight is large, the water vapor barrier property is enhanced, but the adhesive strength to the adherend is lowered. If the weight average molecular weight is small, the adhesive strength is increased, but the vapor barrier property is lowered. If the adhesiveness is excessively poor even if the water vapor barrier property is high, water vapor or impurities will invade from the gap with the adherend, and the resultant organic electronic device element tends to deteriorate unless the additional sealing treatment by the glass frit or the like is performed. If the vapor barrier property is too low even if the adhesive strength is good, even if intrusion of water vapor or the like from the gap can be prevented, the moisture permeates the sealing layer, and consequently, the element for the organic electronic device is easily deteriorated. Further, if the weight average molecular weight is large, the followability to the adherend is lowered, and when sealed, air bubbles enter the adherend and the appearance is damaged. By setting the weight average molecular weight (Mw) to 10,000 to 300,000, it is possible to prevent deterioration of the device for organic electronic devices because of its sufficient vapor barrier property and adhesive strength. In addition, it has good followability to the adherend, and the bubble is not curled when it is sealed, and appearance is improved.

Here, the weight average molecular weight (Mw) can be measured by gel permeation using, for example, a GPC system (column: Shodex K-804 (polystyrene gel) manufactured by Showa Denko KK, mobile phase: chloroform) manufactured by Waters Is the weight average molecular weight in terms of polystyrene measured by chromatography (GPC).

[Hydrogenated cyclic olefin-based polymer (B)]

Examples of the hydrogenated cycloolefin-based polymer include CLEARLON P, M and K series manufactured by Yasuhara Chemical Co., Ltd., Formal AX and S-105 manufactured by Ashland Co., Ltd., Arcon P manufactured by Arakawa Kagaku Kogyo Co., (P-100, P-125, P-140) manufactured by Idemitsu Kosan Co., Ltd., and Eskorez manufactured by Exxon Chemical Co., Ltd. ESR, 5300, 5400, 5600 series), Easttak series manufactured by Eastman Chemical Co., Ltd., and Poral series. Of these, hydrides of C5 series petroleum resins, hydrides of C9 series petroleum resins, Based petroleum resin is suitably used in view of good water vapor barrier performance and transparency.

The number average molecular weight (Mn) by the vapor pressure absolute molecular weight measurement method (VPO method) of the hydrogenated cycloolefin type polymer (B) is preferably 660 or more and 1000 or less. When the number average molecular weight is less than 660, the heat resistance temperature is not increased. When the number average molecular weight is more than 1000, the flexibility at the time of attachment is impaired and the function as the tackifier is sometimes impaired. The softening point in JIS K 2207 is preferably 100 deg. C or higher and 150 deg. C or lower.

The mixing ratio (A) :( B) of the polyisobutylene resin (A) having a weight average molecular weight (Mw) of 10,000 to 300,000 and the hydrogenated cycloolefin polymer (B) is 90:10 to 20:80 , And particularly preferably 70:30 to 30:70. If the mixing ratio of the hydrogenated cyclic olefinic polymer (B) is less than 10, the bonding strength is lowered or the brittleness is increased, and bonding workability is poor when the sealing layer 3 is bonded to a glass substrate or an element substrate of the organic EL element or the like . When the proportion of the polyisobutylene resin (A) having a weight average molecular weight (Mw) of 10,000 to 300,000 is less than 20, the water permeability is increased and the film can not be maintained in shape and torn.

[drier]

The resin composition for sealing an organic electronic device may also contain a desiccant. The desiccant is used for the purpose of trapping moisture permeating through the resin composition. By capturing moisture, deterioration of the element for an organic electronic device by moisture can be further suppressed.

The drying agent may be either a metal oxide drying agent or an organic drying agent, and is not particularly limited. One or more of them may be used in combination.

(Metal oxide-based drying agent)

The metal oxide-based drying agent is usually added to the resin as a powder. The average particle diameter thereof is usually in a range of less than 20 mu m, preferably not more than 10 mu m, more preferably not more than 1 mu m. For example, powdery inorganic oxides such as barium oxide (BaO), calcium oxide (CaO), strontium oxide (SrO), magnesium oxide (MgO), zeolite and molecular sieve (Union Showa K.K. It is possible. As described later, when the resin composition for sealing an organic electronic device is formed into a film, the metal oxide-based drying agent should be sufficiently smaller than its film thickness. By adjusting the particle system in this manner, the possibility of damaging the organic EL element is lowered, and even when provided to a device of the so-called top emission structure, the desiccant particles do not interfere with image recognition. When the average particle diameter is less than 0.01 mu m, the production cost may be increased to prevent scattering of the desiccant particles.

(Organometallic desiccant)

The organic compound may be a material which introduces water by chemical reaction and does not become opaque before and after the reaction. Organometallic compounds are particularly suitable for their drying ability. The organometallic compound in the present invention is defined as a compound having a metal-carbon bond, a metal-oxygen bond, a metal-nitrogen bond, or the like. When the water and the organometallic compound are reacted, the above-mentioned bond is broken by the hydrolysis reaction to form a metal hydroxide.

Examples of preferred organometallic compounds in the present invention include metal alkoxides, metal carboxylates and metal chelates. As the metal, an organometallic compound having good reactivity with water, that is, a metal atom which tends to break various bonds with the above-mentioned metal by water, may be used. Specific examples thereof include aluminum, silicon, titanium, zirconium, silicon, bismuth, strontium, calcium, copper, sodium and lithium. Further, magnesium, barium, vanadium, niobium, chromium, tantalum, tungsten, chromium, indium, iron and the like can be given. In particular, a drying agent of an organometallic compound having aluminum as a central metal is suitable from the viewpoints of dispersibility in a resin and reactivity with water. The organic group may be an unsaturated hydrocarbon such as methoxy, ethoxy, propoxy, butoxy, 2-ethylhexyl, octyl, decyl, hexyl, octadecyl or stearyl, A branched saturated hydrocarbon, a cyclic hydrocarbon-containing alkoxy group, a carboxyl group, an acetylacetonate group, and a dipivaloylmethanato group.

The amount of the drying agent to be added is preferably 1 wt% to 50 wt% with respect to the total weight of the resin composition for sealing an organic electronic device. When the addition amount is less than 1 wt%, the effect is not exhibited. When the addition amount is more than 50 wt%, the fluidity of the device sealing resin for organic electronic devices is lowered and sealing becomes difficult.

[Plasticizer]

The resin composition for sealing an element for an organic electronic device may also include a plasticizer. The flowability can be changed by introducing a plasticizer. Examples of the plasticizer include esters such as wax, paraffin, phthalic acid ester and adipic acid ester, low molecular weight polybutene, polyisobutylene and the like.

[Other additives]

The resin composition for sealing an element for an organic electronic device may contain a silane coupling agent. By using the silane coupling agent, the amount of chemical bonding to the adherend increases, and the adhesive property is improved.

Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, vinyltrimethoxysilane, N- (2- (vinylbenzylamino) ethyl) 3-aminopropyltrimethoxy Silane coupling agents such as silane hydrochloride and 3-methacryloxypropyltrimethoxysilane. Two or more of these silane coupling agents may be mixed. The content of the silane coupling agent is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 1 part by mass, per 100 parts by mass of the resin composition.

In the present invention, other components such as a preservative stabilizer, an antioxidant, a pressure-sensitive adhesive adjuster, and a resin stabilizer may be further added as long as the object of the present invention can be attained. However, There is a possibility that the visibility of the display device is deteriorated, so care must be taken.

The resin composition for sealing an organic electronic device has a water content of not more than 500 ppm by the Karl Fischer method according to the water vaporization-total amount titration method specified in JIS K 0068. When the water content by the Karl Fischer method is 500 ppm or less, deterioration of the sealed organic electronic device element can be sufficiently slowed.

In order to make the water content by the Karl Fischer method of the resin composition for sealing devices for organic electronic devices to be 500 ppm or less, it is necessary to use a dryer such as a conical dryer or an evaporator, Remove the molecule. The resin composition for sealing an organic electronic device for element sealing is filled into an aluminum laminate bag having a water vapor permeability of not more than 0.1 g / (m < 2 > d) according to JIS Z 0222 so as to absorb moisture in the air, It may be stored in another bag in a sealed state together with a drying agent such as silica gel or calcium oxide or calcium chloride. Or a resin composition for sealing an organic electronic device after removal of moisture and the like is filled and sealed in a glass bottle, a poly bottle, a metal can, and the like, and the aluminum laminate bag having a water vapor permeability of not more than 0.1 g / (m 2 · d) according to JIS Z 0222 With a desiccant such as silica gel or calcium oxide or calcium chloride.

The resin composition for element encapsulation for organic electronic devices has an outgassing amount of 500 ppm or less when heated at 85 캜 for 1 hour, as measured by a gas chromatographic analysis method specified in JIS K 0114. By setting the outgassing amount to 500 ppm or less, deterioration of the sealed organic electronic device element can be sufficiently suppressed. In order to make the outgassing amount to 500 ppm or less, moisture, solvent, and volatile organic molecules in the resin composition may be removed in a dryer such as a conical dryer or an evaporator, or in a drying furnace when processed into a film. It is also possible to fill the aluminum laminate bag and store it in another bag in a sealed state together with a drying agent such as silica gel, calcium oxide, or calcium chloride. Or the resin composition after the removal of a solvent or the like is filled in a glass bottle, a poly bottle, a metal can, or the like, and then sealed in an aluminum laminate bag together with a drying agent such as silica gel, calcium oxide, or calcium chloride.

The resin composition for sealing an organic electronic device preferably has a loss elastic modulus at 60 占 폚 measured by ARES of 100,000 Pa 占 퐏 or less. If the loss elastic modulus is larger than 100,000 Pa sec, the fluidity of the resin is lowered and the followability against the unevenness of the sealing surface is lowered. Therefore, the sealing substrate and the element substrate of the organic electronic device element are sealed with the resin composition for sealing the organic electronic device , The appearance of the joint surface may be deteriorated.

The resin composition for sealing an organic electronic device is preferably colorless transparent in a visible region of 400 to 800 nm and preferably has a light transmittance of 85% or more for light having a wavelength of 550 nm at a thickness of 0.1 mm. When the light transmittance at 550 nm is less than 85%, the visibility is lowered. The light transmittance can be selected by selecting a resin.

The resin composition for sealing an organic EL device may contain a solvent in order to obtain the film-like sealing layer (3). Examples of such a solvent include organic solvents such as toluene, methyl ethyl ketone (MEK), ethyl acetate, dimethylacetamide, N-methyl-2-pyrrolidone and a mixed solution thereof. Methyl ethyl ketone and toluene are particularly preferable Do. A resin solution obtained by adding and dispersing individual materials contained in the resin composition to such a solvent is applied onto the release face of the base sheet 2 by a roll coating method, a gravure coating method, a reverse coating method, a spray coating method, A sealing layer 3 can be obtained by applying and drying the composition by a direct or transfer method according to a generally known method such as a knife coating method, a curtain coating method, a die coating method and a comma coating method.

As a method for obtaining the film-like sealing layer 3 without using an organic solvent, the resin composition for sealing an organic EL device is melted at a high temperature and extruded by a generally known method such as a hot melt coater, Layer 3 can be obtained.

The thickness of the sealing layer 3 is not particularly limited and may be appropriately selected depending on the application. And is usually 10 to 30 占 퐉, preferably 15 to 25 占 퐉. If the thickness is less than 10 mu m, sufficient bonding strength may not be obtained. If the thickness is more than 30 mu m, the area of the side surface of the sealing material exposed to the air after sealing is increased, so that the amount of absorption from the side increases. do.

Further, it is more preferable that both the sealing layer 3 and the surface roughness Ra of the object to be bonded to which the sealing layer 3 is in contact are both 2 m or less. If the surface roughness exceeds 2 탆, there is a high possibility that the sealing layer 3 can not completely follow the surface of the object to be bonded even if the followability of the resin composition for sealing the organic EL device itself is high. Therefore, if the surface roughness is in an appropriate range, the sealing layer 3 and the object to be bonded closely contact each other, thereby improving visibility. The surface roughness of the object to be bonded can be changed by polishing or surface treatment and the surface roughness of the sealing layer 3 can be changed by changing the surface roughness of the cooling roll or changing the surface roughness of the release film 4 Can be changed.

The resin sheet 1 for sealing an organic electronic device may have a sealing layer 3 having two or more layers or a layer other than the sealing layer 3. As a layer other than the sealing layer 3, for example, a gas barrier film, a glass plate, a metal plate, a metal foil, or the like may be pressed and bonded to a surface of the sealing layer 3 opposite to the substrate sheet 2. In this case, the release film 4 may not be provided.

<How to use>

Next, a method of using the resin sheet 1 for sealing an organic electronic device will be described.

The resin sheet (1) for sealing an element for an organic electronic device of the present invention is used for sealing an element for an organic electronic device such as the organic EL element (6). More specifically, the organic EL device 6 is placed between an element for an organic electronic device such as the organic EL element 6 provided on the element substrate 5 (see FIGS. 2 and 3) and the sealing substrate 8 (see FIGS. 2 and 3) , And an element for an organic electronic device is hermetically sealed with the element substrate 5 and the sealing substrate 8 to obtain various organic electronic devices of a solidly sealed structure. Examples of organic electronic devices include organic EL displays, organic EL lights, organic semiconductors, organic solar cells, and the like.

Hereinafter, an organic EL display (image display apparatus) will be described as an example of an organic electronic device. 2, an organic EL element 6 provided on an element substrate 5 is covered with a sealing substrate 8 via a resin layer 7 for sealing an organic EL element, And is sealed.

2, the organic EL element 6 includes a positive electrode 61 formed by patterning a conductive material on an element substrate 5 including a glass substrate or the like, And a cathode 63 formed by patterning a conductive material which is laminated on the upper surface of the organic layer 62 and has transparency. A part of the anode 61 and the cathode 63 extend to the end of the element substrate 5 and are connected to a driving circuit (not shown). The organic layer 62 is formed by laminating a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer sequentially from the anode 61 side, and the light emitting layer is formed by laminating a blue light emitting layer, a green light emitting layer, and a red light emitting layer. Further, the light-emitting layer may have a non-luminescent intermediate layer between the respective light-emitting layers of blue, green, and red.

Further, the sealing side surface of this organic EL display 10 is exposed, and further sealing treatment by glass frit or the like may not be performed. Since the resin composition for sealing an organic electronic device according to the present invention has high water vapor barrier property and adhesiveness, it is not necessary to perform additional sealing treatment using a glass frit or the like. Thus, the structure can be simplified and the cost can be reduced have.

The sealing substrate 8 can be any material that does not significantly impair the visibility of the display contents of the organic EL display 10, and for example, glass, resin, or the like can be used.

The resin layer 7 for sealing an organic EL device is formed by using the resin sheet 1 for sealing an element for an organic electronic device described above and can be formed by the following steps. 3 (A), the release film 4 of the resin sheet 1 for sealing an organic electronic device is peeled off to form the sealing layer 3 (see FIG. 3 Is roll-joined to the sealing substrate 8. [ Next, as shown in Fig. 3C, the base sheet 2 of the resin sheet 1 for sealing an organic electronic device bonded to the sealing substrate 8 is peeled off. 3 (D), the sealing layer 3 of the resin sheet 1 for sealing an organic electronic device for an organic electronic device bonded to the sealing substrate 8 is bonded to the cathode (not shown) of the organic EL element 6 63) side. The sealing layer 3 of the resin sheet 1 for sealing an organic electronic device constitutes the resin layer 7 for sealing an organic EL element in the organic EL display 10. [

The bonding and laminating are preferably performed at a temperature of 100 DEG C or lower. If the temperature exceeds 100 ° C, the constituent material of the organic EL device 6 may be deteriorated and the luminescent characteristics may be deteriorated.

The resin sheet 1 for sealing an organic electronic device is first rolled to the sealing substrate 8 in the step of forming the resin layer 7 for sealing an organic EL device. So that the organic EL device having the sealing layer 3 can be manufactured. In this case, after the base sheet 2 of the resin sheet 1 for sealing an element for organic electronic devices is peeled off, the sealing layer 3 is laminated on the sealing substrate 8.

A gas barrier film may be interposed between the sealing layer 3 and the sealing substrate 8 or an organic electronic device in which a gas barrier film is previously bonded to a surface of the sealing layer 3 opposite to the substrate sheet 2 It is also possible to use the resin sheet 1 for sealing the element for sealing. In the case of using the resin sheet 1 for sealing an organic electronic device for an organic electronic device in which a gas barrier film is previously bonded to a surface of the sealing layer 3 opposite to the substrate sheet 2, The sealing layer 3 is bonded to the organic EL element 6 to prepare an organic EL element provided with the gas barrier film and the sealing layer 3. [

Hereinafter, the structure of the present invention will be described in more detail based on examples, but the present invention is not limited thereto.

(Raw materials)

<Polyisobutylene resin>

A1: Weight average molecular weight 2,300 (Glissopal V1500, BASF)

A2: Weight average molecular weight: 36,000 (Oppanol B10SFN, BASF)

A3: Weight average molecular weight: 285,000 (Oppanol B30SF manufactured by BASF)

A4: weight average molecular weight 800,000 (Oppanol B80, BASF)

&Lt; Hydrogenated cyclic olefin polymer >

B1: hydrogenated petroleum resin, softening point 100 占 폚 (P-100, manufactured by Idemitsu Kosan Co., Ltd.)

B2: hydrogenated petroleum resin, softening point 140 占 폚 (P-140, manufactured by Idemitsu Kosan Co., Ltd.)

B3: C9-based hydrogenated petroleum resin, softening point 95 캜 (Fine Crystal KE311 manufactured by Arakawa Chemical Industries, Ltd.)

<Acrylic resin>

C1: Weight average molecular weight 500,000 (SG-790, manufactured by Nagase ChemteX Corporation)

<Desiccant>

D1: Calcium oxide (Wako Pure Chemical Industries, Ltd.)

D2: Magnesium oxide, average particle diameter 3.5 占 퐉 (Starmarg U, manufactured by KONOSHIMA KAGAKU KOGYO KK)

D3: an organometallic compound (KELOFF EP-2, manufactured by HOF SEYAKU KOGYO Co., Ltd.)

D4: Organic metal compound (ALCH-TR, manufactured by Kawaken Fine Chemicals Co., Ltd.)

D5: hydrophobic synthetic silicon dioxide, average particle diameter 1.4 mu m (Silysia 310 manufactured by Fuji Silysia Kagaku Co., Ltd.)

(Example 1)

(B) was added to 40 parts by weight of a polyisobutylene resin (A) having a weight average molecular weight of 285,000 and a polyisobutylene resin (Oppanol B30SF manufactured by BASF) 20 parts by weight of a hydrogenated petroleum resin (trade name: Imaab (registered trademark) P-100, manufactured by Idemitsu Kosan Co., Ltd., softening point: 100 占 폚) was dissolved in 200 parts by weight of toluene to obtain a clear coating solution. Next, on the exfoliated surface of a silicone-based releasing agent-coated polyester film (SP-PET-03, manufactured by Mitsui Chemicals, Inc.) having a thickness of 38 탆 as a substrate sheet, the coating liquid After applying the entire surface by an applicator, it was dried at 120 DEG C for 2 minutes by a drying oven to form a sealing layer. The thus obtained sealing layer was further laminated on a release face of a 38 占 퐉 silicone-based releasing agent-coated polyester film (SP-PET-01, manufactured by Mitsui Chemicals, Inc.) as a release film to obtain an organic electronic device Thereby preparing a resin sheet for sealing.

(Examples 2 to 9)

The resin sheets for encapsulating devices for organic electronic devices according to Examples 2 to 7 and 9 were produced in the same manner as in Example 1 except that the coating composition was adjusted in the composition shown in Table 1. In addition, the calcium oxide used in Example 8 was put into a mortar with a sufficient amount of toluene to be sufficiently submerged, ground to a sufficient size, and used as a coating liquid. The magnesium oxide used in Example 7 was used as it was since the particle diameter was sufficiently small.

(Comparative Examples 1 to 8)

Resin sheets for encapsulating devices for organic electronic devices according to Comparative Examples 1 to 3 and 5 to 8 were prepared in the same manner as in Example 1 except that the coating composition was adjusted in the composition shown in Table 2. Further, in the same manner as in Example 1 except that the coating composition was adjusted with the formulation composition shown in Table 2 and the drying was carried out in a drying oven at 80 캜 for 2 minutes, the resin sheet for encapsulating an element for organic electronic devices Respectively.

(Assessment Methods)

Evaluation was carried out according to the following evaluation method. The results are shown in Tables 1 and 2.

The resin sheets for sealing an element for an organic electronic device according to Examples 1 to 9 and Comparative Examples 1 to 8 were formed into a sheet having a thickness of 15 탆 for nylon, 15 탆 for polyethylene, 7 탆 for aluminum foil, 15 탆 for polyethylene, (ST-678, manufactured by Yutaka Fine Pak Co., Ltd.) having a moisture permeability of 0.1 g / m 2 · day (40 ° C. and a humidity of 90%) laminated with 50 μm thick laminated and sealed with calcium chloride, Respectively.

<Measurement of water content>

With respect to the sealing layer from which the release film and the base sheet of the resin sheet for sealing an element for organic electronic devices according to each of the Examples and Comparative Examples were peeled off, the water content was measured by the Karl Fischer method according to the water vaporization- Respectively. The set heating temperature is 150 ° C.

&Lt; Measurement of out gas amount >

The release film of the resin sheet for sealing an organic electronic device for each of the examples and comparative examples and the sealing layer from which the substrate sheet was peeled were measured by a gas chromatographic analysis method specified in JIS K 0114. When the sealing layer was heated at 85 캜 for 1 hour, the volatilized components were collected by a headspace sampling device and measured. Volatile components were calculated in terms of toluene.

<Measurement of dynamic viscoelasticity>

Using a dynamic viscoelastic device (ARES device, manufactured by Rheometric Scientific Company), the release layer of the resin sheet for sealing an organic electronic device for each of the examples and the comparative example, and the sealing layer from which the base sheet was peeled, Temperature rate of 0.1 Hz, rate of temperature increase of 10 캜 / min, and deformation amount of 0.3%, and the loss elastic modulus G "at 60 캜 was obtained.

<Measurement of Adhesion to Glass>

The release film of the resin sheet for sealing an element for organic electronic devices according to each of the Examples and Comparative Examples was peeled off, and a polyester film (Tetron Film G2-C, manufactured by Daikin DuPont Film Co., Ltd.) And rolled at 80 캜 was used as a test piece. The sealing layer sides of the obtained test pieces were roll-bonded to a glass-free alkali glass for LCD (OA-10G, manufactured by Nippon Denshikkusu Kabushiki Kaisha) at a bonding temperature of 80 占 폚 and subjected to 180 占 peeling method specified in JIS Z 0237 Were measured.

&Lt; Glass bonding test (sealing appearance) >

The release film of the resin sheet for sealing an organic electronic device for an organic electronic device according to each of Examples and Comparative Examples was peeled off and the side of the sealing layer was laminated on a 0.5 mm-thick glass for alkali-free glass for LCD (OA-10G manufactured by Nippon Denshi Glass Co., Ltd.) 60 DEG C and 0.1 MPa. Thereafter, the substrate sheet was peeled off, and its peeling surface was vacuum bonded to the glass substrate at 60 DEG C and 0.2 MPa for 2 seconds to prepare a glass bonded sample. The obtained glass bonded specimen was visually evaluated for its sealing appearance. Those containing no bubbles having a maximum width of 0.1 mu m or more and those containing bubbles having a maximum width of 0.1 mu m or more were indicated as &quot; Good &quot;

<Life Evaluation of Organic EL Device>

A commercially available glass substrate provided with ITO was used for etching while leaving the electrode portion, and then subjected to ultrasonic cleaning and UV ozone cleaning at 45 占 폚 for 10 minutes. Subsequently, an organic layer and a negative electrode were formed with a vacuum evaporator to prepare an organic EL element having a size of 19 mm square. The composition of the organic EL device was glass substrate / ITO (300 nm) / NPB (30 nm) / Alq3 (40 nm) / Al-Li (40 nm) / Al (100 nm). Then, the release film of the resin sheet for sealing an organic electronic device for an organic electronic device according to the examples and the comparative examples was peeled off and bonded to an aluminum foil (Mitsubishi Aluminum Kabushiki Kaisha, Mitsubishi Foil tough) having a thickness of 17 탆 on the surface of the sealing layer . Thereafter, the substrate sheet was peeled off, the sealing layer surface was placed on the upper surface of the cathode of the organic EL element, and the pressure was applied at 80 占 폚 and 0.1 MPa pressure for 1 minute to prepare a model of the organic EL display. The half-life period (unit: hour (hr)) at which the initial luminance is halved at an electric current of 2 mA is calculated by using an organic EL light emission efficiency measuring device (EL1003, manufactured by Precision Gauging Co., Ltd.) Respectively. As a result, it was found that the present invention has excellent effects.

<Method of measuring light transmittance>

The light transmittance can be obtained by measuring the light amount of transmitted light by using a spectrophotometer (manufactured by Hitachi High-Technologies Corporation, optical spectrophotometer U-4100 type solid sample measurement system). The release film on one side of the resin sheet for sealing an organic electronic device for each of the Examples and Comparative Examples was peeled off and bonded to an alkali-free glass for LCD (OA-10G, manufactured by Nippon Denki Glass Co., Ltd.) After bonding at a temperature of 80 캜, another release film was peeled off as a measurement sample, and measurement was carried out by using the alkali-free glass for LCD as a reference.

1: Resin sheet for encapsulating devices for organic electronic devices
2: substrate sheet
3: sealing layer
4: release film
5: element substrate
6: Organic EL device
10: organic EL display
61: anode
62: organic layer
63: cathode
7: Resin layer for sealing organic EL devices
8: sealing substrate

Claims (1)

(A) having a weight-average molecular weight (Mw) of 10,000 to 300,000 and a hydrogenated cycloolefin-based polymer (B)
Wherein the composition has a water content of 500 ppm or less by the Karl Fischer method and an outgassing amount of 500 ppm or less when heated at 85 占 폚 for 1 hour.

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